Aqueous dispersions of crystalline polymers and uses

ABSTRACT

Aqueous dispersions of crystalline polymers based on hydrophobic monomers, preferably on a mixture of hydrophobic and hydrophilic monomers which contains a crosslinking monomer, particularly side chain crystalline (SCC) polymers. The dispersions are useful for providing coatings on substrates, particularly on seeds (whose dormancy is thus extended) and on fibrous substrates, particularly human hair (which thus becomes heat-settable).

This application is a continuation of commonly assigned, applicationSer. No. 09/210,421, filed Dec. 11, 1998 now abandoned. Application Ser.No. 09/210,421 is a continuation-in-part of application Ser. No.08/766,865, filed Dec. 12, 1996, now abandoned; application Ser. No.08/769,639, filed Dec. 12, 1996, now abandoned; and application Ser. No.08/929,750, filed Sep. 15, 1997 now U.S. Pat. No. 6,199,318; Thisapplication also claims priority under 35 U.S.C. 365 (a) and 35 U.S.C.119 from PCT Application No. PCT/U.S. 97/22772, filed Dec. 12, 1997. Thedisclosure of each of those applications is incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to aqueous dispersions of crystalline polymers,methods for making such dispersions and the use of such dispersions forcoating substrates.

It is known to use certain organic polymers to provide coatings on awide variety of substrates, including hair (see U.S. Pat. Nos.4,196,190; 4,452,216; 4,834,968 and 4,983,383); fabrics (see U.S. Pat.Nos. 3,644,241; 3,833,393 and 4,780,499); and seeds and other organisms(see U.S. Pat. No. 5,129,180). It is also known to set a fabric byimpregnating the fabric with a monomer component, and polymerizing themonomer while maintaining the fabric in a desired configuration (seeU.S. Pat. No. 4,401,688).

One class of polymers which has been used for coating substratescomprises side-chain crystalline (“SCC”) polymers. However, the knowncoating compositions containing SCC polymers have the disadvantage thatthe polymer is dissolved in an organic solvent. Organic solvents areexpensive, require environmental controls, and are particularlyundesirable for application to human hair or to an organism.

Attempts have been made to prepare aqueous dispersions of SCC polymers(see British Polymer Journal 20, 521-524 (1988), U.S. Pat. Nos.5,506,307 and 5,516,865, and Japanese Patent Document No. 6-192341), butthe results have been poor and/or the techniques expensive.

SUMMARY OF THE INVENTION

We have discovered, in accordance with the present invention, that veryvaluable results can be achieved by coating substrates with aqueousdispersions of polymeric particles in which the polymer is a crystallinepolymer containing units derived from at least one hydrophobic monomerand preferably also from a lesser amount of units derived from at leastone hydrophilic monomer. Particularly useful results are obtained whenthe substrate is a seed or other organism, or a fibrous material. Wehave also discovered, in accordance with the invention, novel aqueousdispersions of crystalline polymers and methods of making suchdispersions.

In one of its embodiments, this invention provides a substrate having asolid polymeric coating thereon, the coating having been obtained by:

(1) applying to the substrate an aqueous dispersion of solid particlescomprising a crystalline polymer, the polymer (a) having a melting pointT_(m) and (b) comprising units derived from a hydrophobic monomer, and

(2) evaporating water from the dispersion to form the solid polymericcoating;

the coating having at least one of the following characteristics:

(A) at temperatures below T_(m), the coating is substantiallyimpermeable to water (as hereinafter defined), and at temperatures aboveT_(m), the coating is substantially permeable to water (as hereinafterdefined);

(B) the polymer is a crosslinked polymer having a gel content of atleast 50%,

(C) the polymer is derived from a monomer component comprising:

(i) a hydrophobic monomer component comprising a first hydrophobicmonomer, the first hydrophobic monomer being such that a homopolymerthereof is crystalline and has a melting point T_(c), and

(ii) a hydrophilic monomer component comprising a hydrophilic monomer,the ratio by weight of the hydrophobic monomer component to thehydrophilic monomer component being 10:1 to 50:1;

(D) the polymer is derived from a monomer component comprising ahydrophobic monomer component comprising (i) a first hydrophobicmonomer, the first hydrophobic monomer being such that a homopolymerthereof is crystalline and has a melting point T_(c), and (ii) a secondhydrophobic monomer which

(a) is such that a homopolymer thereof is amorphous and has a glasstransition point T_(g) which is less than T_(c), and

(b) is present in amount such that T_(m) is (T_(c)−5)° C. or less;

(E) the polymer is derived from a monomer component comprising ahydrophobic monomer component comprising (i) a first hydrophobicmonomer, the first hydrophobic monomer being such that a homopolymerthereof is crystalline and has a melting point T_(c), and (ii) a secondhydrophobic monomer which

(a) is such that a homopolymer thereof is amorphous and has a glasstransition point T_(g) which is more than T_(c), and

(b) is present in amount such that the coating has a tack at (T_(c)+10)°C. which is less than the tack at (T_(c)+10)° C. of a coating formedunder the same conditions from a composition which is identical exceptthat the crystalline polymer does not contain units derived from thesecond hydrophobic monomer;

(F) the polymer is derived from a monomer component comprising:

(i) a hydrophobic monomer component comprising a hydrophobic monomer,the hydrophobic monomer being such that a homopolymer thereof iscrystalline and has a melting point T_(c);

(ii) a hydrophilic monomer component comprising a hydrophilic monomer;and

(iii) a crosslinking monomer having at least two polymerizable groups;

(G) the polymer is derived from a monomer component comprising one ormore monomers containing carboxyl groups, at least 75% of the carboxylgroups having been neutralized;

(H) the polymer is crosslinked by an external crosslinker (as herinafterdefined);

(I) the particles of the dispersion have coalesced to form a continuouscoating, but retain a particulate character;

(J) the coating contains less than 1% of unreacted monomer, based on theweight of the polymer; and

(K) at least some of the particles comprise a core comprising saidcrystalline polymer and a coating around the core comprising asubstantially amorphous polymer.

In describing the invention below, unless otherwise noted, parts,percentages and ratios are by weight. The monomers from which thecrystalline polymer is derived are important. The term hydrophobicmonomer is used herein to denote a monomer whose solubility in water at25° C. is less than 2%. The term hydrophilic monomer is used herein todenote a monomer whose solubility in water at 25° is 2% or more. Morethan one hydrophobic monomer can be used, and the term hydrophobicmonomer component is used herein to denote all the hydrophobic monomerscollectively, and is often abbreviated herein to “BMC.” More than onehydrophilic monomer component can be used, and the term hydrophilicmonomer component is used herein to denote all the hydrophilic monomerscollectively, and is often abbreviated herein to “PMC.” The monomersfrom which the crystalline polymer is derived can include one or moremonomers which contain two or more polymerizable groups, so that thepolymer is crosslinked. Such monomers (which may be hydrophobic orhydrophilic) are referred to herein as crosslinking monomers; and theterm crosslinking monomer component is used herein to denote all thecrosslinking monomers collectively, and is often abbreviated herein to“XLC.” Except where otherwise noted, percentages of monomers givenherein (both as starting materials, and as residual monomers) are basedon the total weight of the monomer starting material. As furtherdiscussed below, the monomers used in preparing the crystalline polymersare preferably n-alkyl acrylates or methacrylates. The abbreviation CnAand 'CnMA are used to denote n-alkyl acrylates and n-alkylmethacrylates, respectively, in which the n-alkyl group contains xcarbon atoms. For example C4A denotes butyl acrylate, and C12MA denoteslauryl methacrylate.

Crystalline melting points given herein (T_(m) and T_(c)) are the peakof a curve produced using a differential scanning calorimeter (DSC) at aheating rate of 10° C. per minute, and using the second heat cycle. Theonset of melting (T_(o)) is taken from the same curve. T_(o), T_(m) andT_(c) are measured in the conventional way well known to those skilledin the art. Thus T_(m) and T_(c) are the temperature at the peak of theDSC curve, and T_(o) is the temperature at the intersection of thebaseline of the DSC peak and the onset line, the onset line beingdefined as the tangent to the steepest part of the DSC curve below thepeak. Tack values given herein are measured as follows. The latex isapplied to a polymeric film (a polyester film available from DuPontunder the trade name “Mylar,” or a filled polyolefin film available fromPPG under the trade name “Teslin”), at a rate such that after thecoating has been dried at 65° C. for 2 hours, it has a thickness ofabout 30 microns. Two such films are laminated together at 35° C. andthe tack is measured with a vslip/peel tester at 230 cm/min.

In a first preferred aspect, this invention provides a method oftreating an organism to extend its dormancy, the method comprising (1)applying to the organism a non-phytotoxic coating composition whichcomprises (a) water, and (b) suspended in the water, particles whichcomprise a crystalline polymer having a melting point T_(m) of 0° to 40°C.; and (2) causing water to evaporate from the composition, therebyforming on the organism a coating which (a) at temperatures below T_(m)is substantially impermeable to water and (b) at temperatures aboveT_(m) is substantially permeable to water.

In a second preferred aspect, this invention provides a compositionwhich comprises:

(a) water,

(b) suspended in the water, particles comprising a crosslinkedcrystalline polymer which

(i) has a gel content of at least 50%,

(ii) contains less than 1% of unreacted monomer, and

(iii) is derived from a monomer component comprising:

1) a hydrophobic monomer component comprising a first hydrophobicmonomer, the first hydrophobic monomer being such that a homopolymerthereof is crystalline and has a melting point T_(c), and

2) a hydrophilic monomer component comprising a hydrophilic monomer, and

3) a crosslinking monomer having at least two polymerizable groups; and

(c) a surfactant.

In a third preferred aspect, this invention provides a method of makinga composition in accordance with the second preferred aspect, the methodcomprising:

(a) providing an aqueous reaction medium comprising:

(i) water,

(ii) the monomer component, the monomer component containing at least 2%of the hydrophilic monomer component,

(iii) the surfactant, and

(iv) at least 1% based on the water, of a cosolvent which increases thesolubility of the hydrophobic monomer component in the water;

(b) polymerizing the monomer component in the aqueous reaction medium sothat at least 99% thereof polymerizes to form the crystalline polymer inthe form of particles having an average particle size less than 0.5microns, the monomer component being present in amount such that at theend of the polymerization, the solid polymer content of the reactionmixture is at least 30%; and

(i) the surfactant being present in amount such that the monomercomponent is initially present in the aqueous reaction medium in theform of droplets having a diameter greater than 10 microns, and/or

(ii) the surfactant and the cosolvent being present in amount such thatthe hydrophilic monomer component is substantially randomly polymerizedin the crystalline copolymer.

In a fourth preferred aspect, this invention provides a method forpreparing an aqueous suspension, the method comprising the steps of:

(a) providing an aqueous reaction medium comprising:

(i) water,

(ii) a first monomer component comprising a hydrophobic monomercomponent comprising a first hydrophobic monomer, the first hydrophobicmonomer being such that a homopolymer thereof is crystalline, and

(iii) a surfactant;

b) polymerizing the first monomer component to form a crystallinepolymer in the form of particles suspended in the reaction mixture; and

c) polymerizing a second monomer component to form a shell on saidparticles,

the amounts of said first and second monomer components being such thatthe product of step (c) has a solids content of at least 30%, and

the amount of surfactant being such that the product of step (c)contains particles having an average particle size of less than 0.5microns and a residual monomer content of less than 1%.

In a fifth preferred aspect, this invention provides a compositionsuitable for use in setting a fibrous material, the compositioncomprising:

(a) water;

(b) particles suspended in the water, the particles comprising acrystalline polymer; and

c) an effective amount of an additive having a desired effect on thefibrous material. The term “effective amount” is used herein to denotean amount which is sufficient to provide the fibrous material withdesired benefits, taking into consideration the thickness, density,length and texture of the fibers.

In a sixth preferred aspect, this invention provides a method of coatinga fibrous material, the method comprising:

(1) applying to the fibrous material a composition in accordance withthe fifth aspect of the invention; and

(2) evaporating the water from the composition while the composition isin contact with the fibrous material, thereby forming a coating on thefibrous material.

This method can further comprise:

(3) while the coating is at a temperature above T_(m), setting thefibrous material into a first desired configuration; and

(4) cooling the coating to below T_(m) while maintaining the fibrousmaterial in the first desired configuration.

If desired, the method can further comprise:

(5) reheating the coating to a temperature greater than T_(m);

(6) after reheating the coating, and while the coating is at atemperature above T_(m), setting the fibrous material into a seconddesired configuration which is the same as or different from the firstdesired configuration; and

(7) cooling the coating while maintaining the fibrous material in thesecond desired configuration.

The term “cooling the coating” includes merely leaving the coatedmaterial to cool in the ambient atmosphere, as well as methods in whichactive steps are taken to effect cooling. Fibrous materials which can beused include hair, particularly human hair, and woven, knitted andnon-woven fabrics and other textile products such as grains, includingcotton and cotton/polyester blend materials.

It is to be understood that in the foregoing description of theinvention, and in the more detailed description set forth below, thevarious features which are disclosed may be used in any appropriatecombination, and features which are disclosed in connection with aparticular embodiment can be used singly or in combination in connectionwith the invention in general and in connection with other embodiments,except of course where the features are mutually exclusive.

DETAILED DESCRIPTION OF THE INVENTION

A. Materials for Use In The Preparation of the Polymeric Dispersions

In order to prepare the aqueous polymeric dispersions which form part ofthe present invention, and/or which can be used to coat substrates inaccordance with the invention, a monomer component is dispersed in waterwith the aid of a surfactant and preferably a cosolvent; optionallyother additives may also be present. The reaction mixture is thensubjected to conditions which cause the monomer(s) to react to form apolymer which remains in suspension in the reaction medium. The monomercomponent comprises a hydrophobic monomer component (BMC) and preferablyalso a hydrophilic monomer component (LMC). Either the BMC or the LMC,or both, can include a crosslinking monomer. The reaction mixture canalso contain a crosslinking agent, which can be (a) a crosslinkingmonomer component (XLC) which comprises at least one monomer containingat least two polymerizable groups, or (b) an “external crosslinker.” Anexternal crosslinker is a compound which increases the apparentmolecular weight of the polymer without becoming a covalently bound partof the polymer, and which increases the mechanical strength of coatingsformed from the aqueous dispersion of the polymer.

1. Monomer Components

(a) Hydrophobic Monomer Component (BMC)

The BMC comprises at least one first hydrophobic monomer such that ahomopolymer thereof is crystalline and has a melting point T_(c). It mayalso be desirable for the BMC to include at least one second hydrophobicmonomer such that a homopolymer thereof is amorphous and has a glasstransition point T_(g). In one embodiment, T_(g) is less than T_(c) andthe second hydrophobic monomer is present in amount such that the T_(m)of the polymer is (T_(c)−5)° C. or less. In another embodiment, T_(g) ismore than T_(c), in which case the amount of the second hydrophobicmonomer is preferably such that a coating formed from the compositionhas a tack at (T_(c)+10)° C. which is less than the tack at (T_(c)+10)°C. of a coating formed under the same conditions from a compositionwhich is identical except that the crystalline polymer does not containunits derived from the second hydrophobic monomer. The amount of thesecond hydrophobic monomer is generally less than 50%, preferably 5 to40%, particularly 5 to 30%, based on the BMC.

Preferred hydrophobic monomers are α, β-ethylenically-unsaturatedmonomers, particularly n-alkyl acrylates and n-alkyl methacrylates inwhich the n-alkyl groups contains 4 to 24 carbons.

Preferred first hydrophobic monomers are monomers whose homopolymers areside chain crystalline (SCC) polymers. SCC polymers are well known, andare described for example in the following publications, to whichreference should be made for a more complete disclosure of firsthydrophobic monomers suitable for use in this invention: J. Poly. Sci.60, 19 (1962), J. Poly. Sci. (Polymer Chemistry) 7, 3053 (1969), 9,1835, 3349, 3351, 3367, 10, 1657, 3347, 18, 2197, 19, 1871, J. Poly.Sci., Poly Physics Ed 18 2197 (1980), J. Poly. Sci. Macromol. Rev. 8,117 (1974), Macromolecules 12, 94 (1979), 13, 12, 15, 18, 2141, 19, 611,JACS 75, 3326 (1953), 76, 6280, Polymer J 17, 991 (1985), Poly. Sci USSR21, 241 (1979), U.S. Pat. Nos. 4,380,855, 5,120,349, 5,129,180,5,156,411, 5,254,354, 5,387,450, 5,412,035, 5,469,869, and 5,665,822.Particularly preferred first hydrophobic monomers are those which resultin SCC polymers in which the side chain comprises a linear polymethylenegroup containing 12 to 50, preferably 14 to 22, carbons, or a linearperfluorinated or substantially perfluorinated polymethylene groupcontaining 6 to 50 carbons. Mixtures of such hydrophobic monomers can beused. Preferred monomers are those which are commercially available, inparticular the n-alkyl acrylates. Preferred first hydrophobic monomersfor use in the invention comprise at least one of C12MA, C12A, C14A,C14MA, C16A, C16M, C18A, mixtures of C18A, C20A and C22A, mixtures ofC26A and C40A, fluorinated C8A, and mixtures of fluorinated C8A, C10Aand C12A, and other monomers which produce substantially the same finalpolymers, e.g. acrylamides and methacrylamides.

Preferred second hydrophobic monomers are monomers whose homopolymershave a T_(g) of −50 to 120° C., for example n-butyl, isobutyl, andtertiary butyl methacrylates, vinyl acetate, vinyl propionate, n-butyland t-butyl acrylates, homopolymers of which have T_(g)S of 32, 65, 107,28, 10, 40, and 52° C., respectively. Examples of suitable secondhydrophobic monomers are linear and branched chain alkyl, hydroxyalkyland alkoxyalkyl acrylates, methacrylates, acrylamides, andmethacrylamides, and vinyl esters, in particular C8A, C8MA, 2-ethylhexylacrylate and methacrylate, C6A, C6MA, C4A, C4MA and mixtures thereof.

(b) Hydrophilic Monomer Component (LMC)

The LMC comprises at least one hydrophilic monomer and is preferablypresent in an amount of 2 to 10%, particularly 2 to 5%. The hydrophilicmonomer is preferably an αβ-ethylenically unsaturated monomer, forexample a vinylic compound such as acrylic acid; methacrylic acid; analkyl, hydroxyalkyl or alkoxyalkyl acrylate or methacrylate (e.g.hydroxy ethyl methacrylate); acrylamide and methacrylamide; acrylic ormethacrylic acid; acrylamide; methacrylamide; maleic anhydride; itaconicacid; a comonomer containing an amine group; and2-acrylamido-2-methylpropane sulfonic acid (AMPS) and combinationsthereof. Preferably the hydrophilic monomer is selected from the groupconsisting of acrylic acid, methacrylic acid, itaconic acid,2-acrylamido-2-methylpropane sulfonic acid, acrylamide, methacrylamide,or hydroxyethyl (meth)acrylate or a mixture thereof.

(c) Crosslinking Monomer Component (XMC)

The XMC, if present, comprises at least one crosslinking monomer whichcontains at least two polymerizable groups, e.g. vinylic groups. The XMCis preferably used in amount such that the polymer has a gel content ofat least 50%, particularly at least 60%, up to substantially 100%.Preferred hydrophobic crosslinking monomers include 1,4-butanedioldiacrylate, 1,6-hexanediol diacrylate, 1,14-tetradecyidiol diacrylate,divinyl benzene, vinyl crotonate, divinyl ether, and 1,3,5-triallyltriazine trione, and mixtures thereof. Preferred hydrophiliccrosslinking monomers include ethylene glycol diacrylate, and ethyleneglycol dimethacrylate, and mixtures thereof.

The amount of crosslinking monomer is preferably such that the polymerhas a crosslink density (number of crosslinks per weight averagemolecular weight) of at least 0.01, preferably at least 0.05,particularly at least 0.1, so that the polymer resists flow above T_(m).A high gel content (e.g. crosslinking beyond 1 to 10 mole percent) isnot generally needed and can result in decreased crystallinity and poorperformance. The crosslinked polymer preferably has a heat of fusion ofat least 10, preferably at least 20, J/g.

The use of an XMC is important when it is desirable for the coating tobe easily removed, because the resulting crosslinked polymer particlesare harder; and when water is evaporated from dispersion, the particlesdo not easily diffuse into each other. The resulting coatings have aparticulate character and as a result are more easily removable andfrangible. This is particularly important for hair-setting compositions,since it is desirable that the film-forming material be removable bywashing hair with water. It is also particularly important for seedcoatings; prior art non-particulate coatings can remain on the seed andinhibit seed germination. In the absence of crosslinking, when the wateris evaporated, the latex particles are brought together by capillaryaction, and the water is squeezed out from the interstitial spaces. Theparticles coalesce and lose their identity, and a substantially uniformfilm results.

(d) Carboxyl-Containing Monomer Component

The monomer component can contain one or more monomers containingcarboxyl groups, the carboxyl groups being partially, preferably atleast 75%, neutralized (e.g. with NaHCO₃) after the polymerization iscomplete.

(e) Preferred Monomer Components

Preferred monomer components result in a crystalline polymer having asharp melting point, preferably such that (T_(m)−T_(o)) is less than 20°C., preferably less than 15° C., particularly less than 10° C., whereT_(o) is the onset of melting on the DSC curve. Particularly preferredmonomer components comprise:

(i) 50 to 100%, preferably 65 to 95%, of at least one first hydrophobicmonomer which is an alkyl acrylate, alkyl methacrylate, alkylacrylamide, alkyl methacrylamide, alkyl vinyl ether or alkyl vinyl esterin which the alkyl group is an n-alkyl group containing 12 to 50 carbonatoms;

(ii) 0 to 35% of at least one second hydrophobic monomer which is analkyl acrylate, alkyl methacrylate, N-alkyl acrylamide, alkyl vinylether, or alkyl vinyl ester in which the alkyl group is an n-alkyl groupcontaining 4 to 12 carbon atoms; and

(iii) at least 2%, and preferably no more than 10% of at least onehydrophilic monomer which is acrylic acid, methacrylic acid,2-acrylamido-2-methylpropane sulfonic acid, hydroxyethyl acrylate ormethacrylate itaconic acid, acrylamide, methacrylamide, acrylonitrile,methacrylonitrile, a tetraalkylammonium acrylate, vinyl acetate orN-vinyl pyrrolidone.

2. External Crosslinkers

External crosslinkers, when used, are generally compounds containingcharged groups which interact with charged groups in the polymer.Preferred external crosslinkers contain metal (e.g. Mg, Mn, Zn, Ca, Tior Zr) cations or bidentate or multidentate amine groups. Other externalcrosslinkers are non-metallic and organic compounds, e.g. triethylenetetramine, ethylene diamine, diethyl aminopropylamine and bis(quaternaryammonium) salts. The amount of external crosslinker is generally 0.1 to10, preferably 0.5 to 3%, based on the monomer component. Some externalcrosslinkers do not have any effect until a coating is prepared from thedispersion. For example, the cation can be present as an ammonia complexand not become effective until the ammonia is removed during theevaporation step. Thus, an aqueous solution containing Zn(NH₃)⁺⁺ ionscan be used in this way.

External crosslinkers can be used in combination with crosslinkingmonomers.

3. Surfactants

The reaction medium for the polymerization comprises at least onesurfactant, preferably at least one ionic surfactant and at least onenon-ionic surfactant, to suspend and stabilize the particles formed bypolymerizing the monomer component in the aqueous reaction medium. Theamount of surfactant can be 0.8 to 10%, preferably 1 to 5%, based on thereaction medium. However, the optimum amount of surfactant depends alsoon the amount of cosolvent present, as further described below.Preferably, sufficient surfactant is present to enable the monomercomponent to be present initially as droplets having a diameter of morethan 10 microns.

Surfactants are characterized by a hydrophile-lipophile balance (HLB)number that describes the strength of the hydrophilicity to thelipophilicity of the surfactant. Anionic surfactants having a HLB numberof 20 to 40 are preferably used, and function to form micelles at lowconcentrations and to act as nucleation sites for the latex particles.Once nucleation is complete, the surfactants can additionally providecharge stabilization to the growing latex particles. Preferably theanionic surfactants contain a sulfate or sulfonate group and ahydrophobic moiety and may be, for example, alkyl sulfates, alkyl ethersulfonates and sulfates, alkylaryl sulfonates, and sulfosuccinates.Preferred anionic surfactants are the amine salt of dodecyl benzenesulfonic acid, salts of dioctyl sulfosuccinate, salts of lauryl sulfate,and salts of the ethoxylated alcohol half ester of sulfosuccinic acid.Exemplary alkyl and alkene sulfonates are described in U.S. Pat. Nos.4,983,383 and 5,194,469.

Nonionic surfactants having HLB numbers of 5 to 35, e.g. 5 to 30,preferably 10 to 15, can also be employed. These surfactants lower theinterfacial tension between the monomer oil droplets and the aqueousphase, and provide stabilization of the polymer dispersion bypartitioning at the interface of the aqueous phase and the polymerparticles. Thus they reduce the polymer dispersion's sensitivity toshear, temperature and the presence of electrolytes. The nonionicsurfactants can be linear or branched ethoxylated alcohols, ethoxylatedalkylphenols, or block copolymers of ethylene oxide and propylene oxide.Preferably they contain 3 to 40 ethylene oxide repeat units and ahydrophobic moiety which may be a linear or branched C₁₁-C₁₅ secondaryalcohol, nonylphenol or octylphenol, or are block copolymers of ethyleneoxide and propylene oxide.

The amount of surfactant present is preferably such that high energyhomogenization of the monomer component is not needed to form the latex.When little or no cosolvent is used, preferably a relatively largeamount of surfactant (e.g. at least 5% based on the monomer component)is used so that the monomer component is dispersed in the reactionmixture as droplets having a diameter greater than 10 microns.

The amount of surfactant and cosolvent in the reaction mixture ispreferably such that the units derived from the second hydrophobicmonomer (if present) and/or the hydrophilic monomer are substantiallyrandomly dispersed in the polymer.

The surfactant can be a polymerizable component which is incorporatedinto the polymer.

The choice of the surfactant may be influenced by the end use of thedispersion. For example, particularly useful surfactants forcompositions used for coating corn seeds are fluorine-containingsurfactants.

4. Cosolvents

The reaction medium preferably contains at least one cosolvent (alsoreferred to as a diffusion modifier) which increases the solubility ofthe hydrophobic monomer in the reaction medium. It is generally presentin amount at least 10% but less than 30%, preferably 5 to 20%, based onthe water. Because the cosolvent increases the water solubility of thehydrophobic monomer, it increases the transport rate of the hydrophobicmonomer from the monomer micelles or oil droplets to polymer nucleationsites. The cosolvents are preferably linear or branched monoalkanolscontaining 1 to 4 carbons, alkyl esters or alkyl ethers containing 1 to6 carbons. Preferred cosolvents have a solubility in water of more than0.7% at 25° C. and have boiling points of 60° to 130° C., preferablyless than 95° C., so that they can be easily removed after thepolymerization reaction. Preferred cosolvents include ethanol,isopropanol, ethyl acetate, n-propanol, sec-butanol, and t-butanol, andcombinations thereof. Preferably the cosolvent has a water-octanolpartition coefficient of at least 0.2 to enhance the solubility of thehydrophobic monomers in the water (see “Handbook of Property EstimationMethods,” edited by W. J. Lyman, W. F. Reehl, D. H. Rosenblatt, AmericanChemical Society, Washington, D.C. 1990).

The amount of cosolvent preferably used depends upon the amount and typeof surfactant used. For example, where there is about 1.6% of ionic andnon-ionic surfactants, at least 5% of the cosolvent is generallyrequired to obtain a single sharp melting point crystalline polymer,whereas when about 0.8% of ionic and non-ionic surfactants is present,at least about 10% of the cosolvent is generally required.

5. Initiators

A free radical initiator must generally be present to cause thepolymerization to take place, generally in amount 0.1 to 0.4% based onthe reaction mixture. Alternatively or additionally, ultravioletradiation can be used to initiate the reaction.

Initiators useful in emulsion polymerization are well known [see, forexample, U.S. Pat. No. 5,516,865 and “Emulsion Polymerization,” Blackley(1975), chapter 6, Applied Science Publishers, London]. Suitablehydrophobic initiators for this invention include benzoyl peroxide anddi-t-butyl peroxide. Suitable hydrophilic initiators include hydrogenperoxide and potassium and ammonium persulfate. A redox initiator, e.g.t-butyl hydroperoxide/ascorbic acid, or hydrogen peroxide/ferrouscompound, can also be used.

6. Other Additives

The reaction mixture can contain a variety of other additives, includingpH adjusters (e.g. sodium hydroxide and ammonium hydroxide); pH buffers(e.g. sodium bicarbonate and sodium hydrogen phosphate); coalescingagents (e.g. N-methylpyrrolidone, poly(ethylene glycol) alkyl ethers andpoly(ethylene glycol); colloidal stabilizers (e.g. hydroxyethylcellulose, polyacrylates and polyvinyl alcohols); rheology modifiers(e.g. hydroxyethyl cellulose and the products available under the tradenames Kelzan and VCAR from Kelco and Union Carbide, respectively); anddefoamers (e.g. the products available under the trade names Surfynoland Anti-foam H-10 Emulsion from Air Products and Dow Corning,respectively. The addition of sodium bicarbonate tends to increaseparticle size.

B. Polymerization Conditions

1. Single Stage Polymerization

The polymerization is generally carried out at 45 to 90° C., preferably60 to 80° C. Lower temperatures decrease the amount of coagulum andincrease particle size uniformity. Preferably the reaction is carriedout under oxygen-free conditions, e.g. under nitrogen. Polymerization ispreferably continued until at least 99% of the monomer component hasbeen polymerized. Typically this takes 1 to 4 hours at about 70° C.

The polymerization is preferably carried out under conditions such thatthe polymer is obtained in the form of particles having an average sizeof less than 1 micron, preferably less than 0.5 micron, particularly0.25 to 0.35 micron (measured by the well known light scatteringtechnique). Small particle sizes are desirable because the dispersionsare more stable, and do not clog spray nozzles. Preferably the amount ofmonomer is such that the reaction product has a solids content of atleast 25%, particularly at least 30%, especially at least 35%. Highersolids content is desirable because less water needs to be evaporated toform a coating, and because the product is less expensive to package andtransport. However, the solids content is generally no more than 45%,because of the tendency of very high solids content dispersions tocoagulate spontaneously.

After the polymerization is complete, the cosolvent, if used, isgenerally removed. At this stage, further additives can be added to thelatex, depending on the intended use of the product.

2. Two Stage Polymerization

In some applications it can be desirable in a first stage to polymerizethe hydrophobic component thereby forming a crystalline copolymer orhomopolymer, and then polymerizing the hydrophilic component in a secondstage. This results in phase-separated particles having a core ofpredominantly (at least 50% by weight) crystalline polymer and a shellaround the core, the shell being formed predominantly of non-crystallinepolymer. Generally, the core is substantially all crystalline polymer asa first phase, and the shell is substantially all non-crystallinepolymer as the shell. This is desirable when there is a need to changethe properties of the crystalline polymer, such as tack, withoutchanging the T_(m). The monomers used to form the shell are not limitedto hydrophilic materials, but can also be monomers such as styrene orbutyl methacrylate.

For a core/shell product, T_(m) is substantially the same as thecrystalline homopolymer formed from the first hydrophobic monomer.

As in the single stage polymerization, the final latex preferably has asolids content of at least 30% and a residual monomer content of lessthan 1%; and the surfactant likewise preferably is present in amountsuch that the latex particles have an average particle size of less than0.1 micron, particularly less than 0.5 micron.

C. Use of the Dispersions

The dispersions can be used to provide coatings on any solid substrate,e.g. fibers, seeds, or a shaped object. They can be applied to thesubstrate by means of conventional coating techniques such as wire-woundrod, direct gravure, offset gravure, reverse roll, air-knife, trailingblade coating, and spray coating. The coating is typically dried at atemperature at least 5° C. above T_(m) of the crystalline polymer, underambient conditions or by the application of heat.

1. Coating of Fibrous Materials

Compositions for treating fibrous materials preferably (a) contain 2 to50% by weight of the particles comprising the crystalline polymer,and/or (b) contain substantially no organic solvents, and/or (c) containless than 1% by weight of residual monomer. Preferably the compositionis a latex prepared as described above, and for many purposes thepolymer has a T_(m) of 20° to 60° C., particularly 40° to 60° C.

The composition can, for example, be dispensed from a pressurizedcontainer, or from a pump spray, or applied by means of a pad. Thecompositions can be used in place of starch, in which case thecrystalline polymer has a T_(m) usually from 40 to 60° C., which enablesthe polymer to be reset with an iron, but does not result in the polymerbecoming reset in a clothes dryer. Alternatively, the polymer can givethe fabric a “permanent press” character, by choosing a polymer having aT_(m) sufficiently high that it does not easily reset, e.g. at least 60°C., preferably at least 80° C. A similar result can be achieved bycrosslinking the crystalline polymer after the fabric has been coated,e.g. by using an external crosslinker.

Compositions for treating fabrics preferably include an effective amountof at least one fabric-treating additive, this term being used to denoteany compound conventionally used to affect the properties of a fabric.The amount of each such additive is preferably at least 0.1% by weightof the composition. Suitable additives include perfumes, scents, stainresisters, optical brighteners, wetting agents, preservatives,softeners, ironing aids (typically 0.05 to 1.5% by weight of a silicone,e.g. dimethyl or methylphenyl silicone or an amine-modified silicone),anti-static agents, and bleaching agents (e.g. as described inKirk-Othmer, Encyclopedia of Chemical Technology, 4th edition, JohnWiley & Sons, volume 4, pages 271 et seq., and 552 et seq.). Thecomposition can also contain a stabilizer, e.g. a naturally-occurringstarch derived from corn, rice, wheat, or tapioca, or a modified starch,or carboxymethyl cellulose or a clay can also be employed.

Compositions for treating hair (particularly human hair, but also hairon a wig, or hair on a doll) preferably include an effective amount ofat least one hair care additive, this term being used to denote anycompound conventionally used in hair treating formulations. The amountof each such additive is preferably 0.01 to 10%, preferably 0.05 to 5%,based on the composition. Suitable additives include sequesteringagents, hair-conditioning agents (e.g. cetyl trimethyl ammoniumchloride, glyceryl monostearate, glycerin, propylene, glycol, sorbitol,urea, isopropyl myristate, balsam, lanolin, spermaceti, and isopropylpalmitate), anti-dandruff agents (e.g. sulfur, salicylic acid,resorcinol, bithionol, chloral hydrate, and zinc pyrithone), reducingagents (e.g. thioglycolates), bleaching agents (e.g. hydrogen peroxide,and perborate and persulfate salts), scents, perfumes, pearlescent aids(e.g. ethylene glycol distearate), preservatives (e.g. benzyl alcohol,methylparaben, propylparaben, imidazolidinyl urea, and esters ofp-hydroxybenzoic acid), thickeners (also known as viscosity modifiers,e.g. methyl cellulose, starches and starch derivatives), coloring agents(e.g. any of the FD&C or D&C dyes), and pH adjusting agents (e.g. citricacid, sodium citrate, succinic acid, phosphoric acid, sodium hydroxide,and sodium carbonate). Other hair care additives are described in the“COSMETIC INGREDIENT DICTIONARY” published by “THE COSMETIC TOILETRY ANDFRAGRANCE ASSOCIATION INC.”, U.S. Pat. No. 5,009,880, and Kirk-Othmer,Encyclopedia of Chemical Technology, 4th Ed., Vol. 12, John Wiley &Sons, pages 881-917.

The pH of the hair-treating composition is typically 3 to 9, preferablyfrom 6 to 7. For application to human hair on a person, T_(m) ispreferably at least 40° C. so that the hair does not become unset athigh ambient temperatures, but generally is no more than 60° C., so thehair can be reset with a hair dryer or curling iron. A particularadvantage of the present invention is that the coatings can be appliedto hair, and the hair can be repeatedly reset. Thus, the hair can be setin a desired configuration, and then by heating the crystalline polymerto a temperature greater than T_(m), the hair can be reset into a seconddesired configuration. However, when the hair is on a wig or a doll, itcan be desirable to set the hair more permanently. In such a case, T_(m)is sufficiently high, preferably at least 60° C. Alternatively, or inaddition, the composition can be externally crosslinked, as describedabove.

When a coating is formed on human hair, it is generally desirable thatthe coating can be easily removed by washing with water. This can beachieved by using a monomer component which contains (a) an XLC asdescribed above, and/or (b) at least 0.5% of at least one amphotericmonomer, and/or (c) a carboxyl-containing monomer component as describedabove.

2. Coating of Seeds or Other Organisms

When seeds or other organisms are coated, the aqueous dispersion shouldbe non-phytotoxic to the organism being coated. The dispersion ispreferably applied by spray coating, the water then being evaporated byexternal heating or under ambient conditions. Other known applicationmethods can be used. The thickness of the coating and the T_(m) of thepolymer are preferably such that the coating is substantiallyimpermeable to water at temperatures below T_(m). Generally, the T_(m)of the polymer is from 0 to 40° C., preferably 10 to 35° C., and isequal to or greater than the lowest temperature at which the seed cangerminate satisfactorily, and less than the highest temperature at whichthe seed can germinate satisfactorily. Preferably T_(m) is substantiallyequal to, or greater than, the optimum germination temperature of theseed. Minimum, optimum and maximum germination temperatures fordifferent seeds are known to, or can be determined by, those skilled inthe art (see, for example, Plant Propagation: Principles and Practice,by Hartman and Kester, 1959). At temperatures above T_(m), the coatingbecomes substantially permeable to water. In this way, the coatingprevents substantial imbibition of water by the seed at too low atemperature, thus preventing “imbibitional chilling injury” andextending the dormancy of the seed, but permits the seed to imbibe waterat temperatures at which germination can take place satisfactorily. Itis not necessary for the coating to be completely impermeable to waterat temperatures below T_(m), and the term “substantially impermeable”should be understood accordingly. For example, the coating preferablyensures that the seed imbibes no more than 21%, more preferably no morethan 17%, particularly no more than 15%, especially no more than 10%, ofwater over a period of 48 hours at temperatures below T_(m). Similarly,the coating need not be completely permeable to water above T_(m) andthe term “substantially permeable” should be understood accordingly. Forexample, the coating preferably has a permeability to water above T_(m)which is at least 2 times, particularly at least 3 times, itspermeability below T_(m). For example, at temperatures above T_(m), thecoating preferably permits the seed to imbibe. 25% or more, particularly60% or more of water over a period of 48 hours at temperatures aboveT_(m).

The permeability of the coating, as well as the value of T_(m) can beadjusted for the needs of the particular seed. For example, for cornseed, the coating preferably prevents the seed from imbibing more than10% of water over a period of 48 hours below T_(m), but permits the seedto imbibe more than 10% of water over a period of 48 hours above T_(m).More than one coating can be applied to the seed.

The polymers used for coating seeds are preferably derived from amonomer component which includes a second hydrophobic monomer. Polymerswhich lack such a monomer tend to be difficult to apply, and to formtacky, relatively poor quality coatings. It is also preferred that themonomer component should contain a crosslinking component and that anexternal crosslinker should be employed. These measures result in acoating which maintains its integrity well below T_(m), but whichdisintegrates easily when the seed expands, and which does not,therefore, interfere with germination and growth. Other measures whichcan be employed for the same purpose are the use of a monomer componentwhich includes (a) at least 0.5% of at least one amphoteric monomer,and/or (b) a carboxyl-containing monomer component.

Although the foregoing description is directed principally to coatingseeds for controlling the dormancy of the seed, the invention is usefulfor other organisms, and other purposes, e.g. to protect organisms fromfungi and insects. Such other organisms include bacteria, embryos, eggs,sprouts, bugs, rhizobium, seedlings, and potato cuttings. Seeds whichcan be coated include vegetable seeds and grain seeds. For example,seeds for canola, maize, cotton, soybean, sugar beets, beans, tomato,potato, tobacco, corn, rice, wheat, sunflower, the brassica family, thesolanaceae family, sorghum, barley, lentils, melons, cucumbers, cabbage,brussels sprouts, beans, and peas.

The composition applied to the organism can contain one or moreadditives, typically in amount 0.01 to 10%, preferably 0.05 to 5%, basedon the composition. Suitable additives include colorants, fillers, soilpH adjusters, nutrients, seed protectors, phytotoxicity inhibitors,herbicides, growth regulators, soil improvers, fungicides, insecticides,growth stimulants, plant hormones, fertilizers, bird repellents,stimulants to accelerate growth, and innoculants. Such additives canalternatively or additionally be applied to the seed separately.

The invention is illustrated in the accompanying drawings, in whichFIGS. 1-6 are DSC curves for polymers prepared in the Examples, asfurther described below, and

FIGS. 7 and 8 are schematic illustrations of a particulate coating 10,made up of coalesced but still identifiable particles 14, on a substrate12, which is a fiber or a seed, respectively.

EXAMPLES

The invention is illustrated by the following examples, some of whichare comparative examples.

Examples 1-16

Examples 1-16 illustrate the preparation of aqueous polymer dispersions.Examples 1, 5, 6, 9 and 10 are less preferred, in that the crystallinepolymer does not have a single, sharply defined melting temperature.

The following abbreviations are used in Examples 1-16 (and in the laterExamples): C6A, hexyl acrylate (amorphous hydrophobic monomer); C12A,dodecyl acrylate, C14A, tetradecyl acrylate, C16A, hexadecyl acrylate,and C18A, octadecyl acrylate (all crystalline hydrophobic monomers);C6DA, 1,6-hexanediol diacrylate, and CD14A, 1,14-tetradecanedioldiacrylate (both crosslinking monomers); AA, acrylic acid, and MA,methacrylic acid (both hydrophilic monomers); C12SH, dodecyl mercaptan(chain transfer agent); SP, sodium persulfate (initiator); PP, potassiumpersulfate (initiator); SBC, sodium bicarbonate (buffer); EAC, ethylacetate (cosolvent); IPA, isopropanol (cosolvent).

The following are surfactants: SDS, sodium dodecyl sulfate; 15-S-7,15-S-9 and 15-S-40 are C₁₁-C₁₅ secondary alcohol ethoxylates which areavailable from Union Carbide under the trade names Tergitol 15-S-7,15-S-9 and 15-S-40, respectively; P1059, an amine salt of dodecylbenzene sulfonic acid which is available from Witco under the trade nameWitconate P1059; EMC, sodium dioctyl sulfosuccinate which is availablefrom Witco under the trade name EMCOL DOSS; SLS-R which is a 30% byweight lauryl sulfate solution in water available from Lonza, Inc underthe trade name Carsonol SLS-R; and A-102 which is a disodium ethoxylatedalcohol half ester of sulfosuccinic acid available from Cytec under thetrade name AEROSOL A-102.

The amounts of each ingredient used in the Examples are shown in Tables1-3.

Examples 1-8 illustrate how addition of cosolvent and high surfactantconcentrations reduce the heterogeneity of emulsion polymerizationreaction products prepared by using at least two different monomercomponents. Examples 1-4 show the effect of the addition of cosolvent inthe presence of high surfactant concentrations on the heterogeneity ofthe polymerization reaction products. Examples 5-8 show the effect ofthe addition of cosolvent in the presence of low surfactantconcentrations on the heterogeneity.

Examples 1-4

Polymers consisting of four monomer components (C16A, C6A, CD14A and MA)were prepared in the presence of a constant amount of surfactant (3.2%)and variable amounts of cosolvent as shown in Table 1. The emulsionpolymerization components were mixed and degassed for 30 minutes. Thepolymerization reaction proceeded for 4 hours at 70° C. under nitrogen.The polymer prepared in comparative Example 1 in the absence ofcosolvent exhibited a broad profile with two peaks on a DSC thermographas shown in FIG. 1. The polymer prepared in Example 2 in the presence of5% by weight ethanol shows a much sharper DSC peak and a lower T_(m).The polymer prepared in Example 3 in the presence of 5% by weight ethylacetate similarly exhibits a sharp peak. Addition of higherconcentrations of ethyl acetate above 5% only has a slight effect on thesharpness of the DSC peak and the T_(m) of the polymer product as shownin FIG. 2.

Examples 5-8

Polymers consisting of three monomer components (C16A, C6A, and MA) wereprepared in the presence of a constant, but lower, amount of surfactant(1.6%) and variable amounts of cosolvent as shown in Table 1. Theemulsion polymerization components were mixed and degassed for 30minutes. The polymerization reaction proceeded for 4 hours at 70° C.under nitrogen. The polymer prepared in comparative Example 5 in theabsence of cosolvent exhibits multiple DSC peaks. The polymer preparedin comparative Example 6 in the presence of 5% by weight ethyl acetateshows a single DSC peak and a lower T_(m). The polymer prepared inExample 7 in the presence of 10% by weight ethyl acetate exhibits asharp peak (FIG. 3). Addition of higher concentrations of ethyl acetateabove 5% only has a slight effect on the sharpness of the DSC peak andthe T_(m) of the polymer product.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 H₂O 200 g 190 g190 g 180 g 200 g 190 g 180 g 160 g C16A 70 g 70 g 70 g 70 g 70 g 70 g70 g 70 g C6A 25 g 25 g 25 g 25 g 25 g 25 g 25 g 25 g MA 5 g 5 g 5 g 5 g5 g 5 g 5 g 5 g C14DA 2 g 1.5 g 1.5 g 1.5 g — — — — 15-S-9 5 g 5 g 5 g 5g 2.5 g 2.5 g 2.5 g 2.5 g P1059 5 g 5 g 5 g 5 g 2.5 g 2.5 g 2.5 g 2.5 gPP 0.4 g 0.4 0.4 g 0.4 g 0.4 g 0.4 g 0.4 g 0.4 g EAc — — 10 g 20 g — 10g 20 g 40 g Ethanol — 10 g — — — — — — DSC broad sharp sharp sharpmultiple broad sharp sharp peak peak peak peak peaks peak peak peakT_(m) (° C.) 30.7 22.5 21.9 21.6 34.8 33.0 32.6 22.4

Examples 9-12

Polymers consisting of two SCC monomer components (C16A and C12A) and MAwere prepared. Both C16A and C12A -based polymers are side chaincrystalline polymers and can be detected by DSC whereas C6A polymers areamorphous and not detectable. The polymers were prepared in the presenceof varying concentrations of surfactants and cosolvents as shown inTable 2. The emulsion polymerization components were mixed and degassedfor 30 minutes. The polymerization reaction proceeded for 4 hours at 70°C. under nitrogen. The polymer prepared in comparative Example 9 in thepresence of a low surfactant concentration (1.2%) in the absence ofcosolvent exhibited two distinct peaks with T_(m)'s at 1.6° C. and 33.7°C. as shown in FIG. 4. The polymer prepared in comparative Example 10 inthe presence of the same amount of surfactant and 5% by weight ethylacetate shows a broad peak with three peaks with the predominant polymerspecies having a T_(m) of 2.7° C. The polymer of Example 11 was preparedin the presence of higher concentrations of surfactant (2.4%).Increasing the surfactant concentration produces a polymer product witha sharp T_(m) at 13.9° C. as shown in FIG. 5. Example 12 shows the useof different monomer components (C14A and C12A) in a reaction mixturesimilar to that of Example 11. Once again only one peak is observed asshown in FIG. 6.

TABLE 2 Ex. 9 Ex. 10 Ex. 11 Ex. 12 H₂O 200 g 190 g 400 g 400 g C16A 35 g35 g 70 g — C14A — — — 95 g C12A 60 g 60 g 120 g 95 g MA 5 g 5 g 10 g 10g 15-S-9 2 g 2 g 8 g 8 g DOSS 2 g 2 g 8 g 8 g PP 2 g 0.4 g 1.6 g 1.5 gEAc — 10 g — — C12SH — — — 0.1 g DSC two peaks broad peak sharp peaksharp peak T_(m) (° C.) 2, 33.7 2.7 13.9 16.1

Examples 13-15

These examples show the large scale preparation of copolymers using themethod described in this invention. Reaction components are shown inTable 3.

In Example 13 the emulsion polymerization components were mixed anddegassed for 30 minutes. The polymerization reaction proceeded for 4hours at 70° C. under nitrogen. The polymer was polymerized in thepresence of a total surfactant concentration of 2.9% in the presence of20% cosolvent. The polymer product exhibited a peak with a T_(m) of11.3° C.

In Example 14 the emulsion polymerization components were mixed anddegassed for 30 minutes. Part of the polymerization reaction mixture(25%) was metered into a 1 liter resin kettle for 10 minutes at a rateof 12 ml/minute. The mixture was polymerized for 15 minutes at 80° C.The rest of the monomer solution was metered over 75 minutes and thepolymerization reaction proceeded for 2 more hours under nitrogen. Thepolymer product exhibited a peak with a T_(m) of 9° C.

In Example 15 all the polymerization components, except for theinitiator, were mixed and degassed. Once the polymerization componentswere heated to 60° C., degassed initiator was added to the reactionmixture. The reaction proceeded for two hours while maintaining theinternal temperature of the mixture at 70° C. After two hours moreinitiator was added to the reaction mixture to drive polymerization tocompletion. The reaction proceeded for a total of 5 hours. The reactionwas cooled overnight. After cooling the product was neutralized to pH 7with ammonium hydroxide and filtered with a 63 micron sieve. The polymerexhibited a single sharp peak at 9.2° C.

TABLE 3 Ex. 13 Ex. 14 Ex. 15 H₂O 800 g 320 g 4308 g C14A 405 g 160 g2080 g C6A 70 g 30 g 390 g C6DA — 1.4 g 18.2 g MA 25 g 5 g 130 g AA — 10g — A-102 20 g 8 g 104 g SLS 10 g 4 g 52 g 15-S-7 10 g 4 g 52 g 15-S-402.5 g 4 g 13 g PP 2 g 0.8 g 15.6 g SBC 2 g 0.8 g 10.4 IPA 200 g 80 g1040 g DSC sharp peaks sharp peak sharp peak T_(m) (° C.) 11.2 9.1 9.2

Example 16

A polymer was prepared with 2-acrylamido-2-methylpropane sulfonic acid(AMPS, available from Lubrizol) as follows. C16A (31.5 g), AMPS (6 g ofa 50% aq. solution), water (80 g), isopropanol (20 g), Aerosol A-102 (2g), Carsonol SLS-R (1 g) were mixed together and purged with N₂ for 20min. The bottle was then capped and heated to 80° C., and 0.4 g ofpotassium persulfate was added. The reaction was carried out at 80° C.for 3 h. A bluish tan emulsion was formed, cooled overnight andneutralized with ammonium hydroxide.

Examples 17-24

Examples 17-24 illustrate the preparation and use of aqueous polymerdispersions for coating fibers. The molecular weights (which are givenas M_(n) values, i.e. number average molecular weights, or M_(w) values,i.e. weight average molecular weights) were measured by the standard GPCtechnique in tetrahydrofuran, against polystyrene standards. Thefollowing additional abbreviations are used in these and later Examples.C4A, butyl acrylate (amorphous monomer); ESH, mercaptoethanol (chaintransfer agent); AIBN, azobisisobutyronitrile (initiator); ESP,t-amylperoxy 2-ethyl hexanoate which is available from WITCO under thetrade name Esperox 570 (initiator); TERG, a C₁₁-C₁₅ secondary alcoholethoxylate which is available from Union Carbide under the trade nameTergitol 15-S-9 (surfactant).

Example 17

A mixture of C18A (1865 g), MA (150 g)) and C12SH (1 g) was added over aperiod of 20 minutes to a reaction vessel which was purged withnitrogen, stirred, and maintained at 100° C. Over the same period, ESP(10 g) was added separately. After 5 hours, the temperature was raisedto 120° C., and heating continued for a total reaction time of 23 hours.The resulting white polymer had an M_(w) of 198,000, M_(n) of 26,000,T_(o) of 43° C. and T_(p) of 45° C.

Example 18

A sample of the polymer produced in Example 17 was finely ground and wasadded to a mixture of water (90 ml), TERG (1.25 g) and P-1059 (1.25 g)which was maintained at 80° C. in a stirred reaction vessel. After 2hours of mixing, a stable emulsion had been produced.

Example 19

A mixture of C18A (95 g), MA (5 g) and C12SH (0.05 g) was added to amixture of water (200 ml), TERG (5 g) and EMC (5 g) which was maintainedat 80° C. in a stirred reaction vessel. After degassing with nitrogenfor 30 minutes, PP (0.4 g) was added. Heating was maintained for 4hours, and after the reaction mixture had cooled slowly to roomtemperature, it was neutralized with 10% aqueous ammonium hydroxide. Theresulting milky white polymer had a T_(o) of 43° C., T_(p) of 47° C.,and a M_(w) above 1,500,000.

Example 20

A mixture of C16A (400 g), C12A (90 g), AA (10 g) and C12SH (105 g) wasadded over a period of 10 minutes to a reaction vessel which was purgedwith nitrogen, stirred, and maintained at 110° C. Over the same period,ESP (5 g) was added separately. Heating was continued for 4 hours. Theresulting polymer had an M_(w) of 2300, M_(n) of 1500, T_(o) of 21° C.and T_(p) of 28° C.

Example 21

A mixture of toluene (200 ml), C18A (89 g), C16A (11 g), ESH (3.6 g) andAIBN (1 g) was heated under nitrogen at 60° C. for 16 hours and then at80° C. for 2 hours. Isocyanatoethyl methacrylate (8 g) and dibutyl tindilaurate (1 drop) were then added, and heating continued at 60° C. for4 hours. The resulting polymer was precipitated by the addition ofethanol and was a white polymer having an M_(w) of 5300, M_(n) of 4080,T_(o) of 39° C. and T_(p) of 45° C.

A part of the resulting polymer (20 g), C4A (30 g), AIBN (0.5 g), ethylacetate (50 ml) and heptane (50 ml) were heated under nitrogen at 60° C.for 16 hours. The resulting polymer was precipitated by the addition ofethanol and was a white thermoplastic elastomer having an M_(w) of516,000, M_(n) of 34,000, T_(o) of 39° C. and T_(p) of 44° C.

Example 22

The procedure of Example 19 was followed except that one portion(Portion A) of the cooled reaction mixture was not neutralized andanother portion (Portion B) was treated with enough sodium hydroxide toneutralize 50% of the carboxyl groups. Samples of the resulting latexwere tested as follows. 300 mg samples of the latex (containing 100 mgof the polymer) were placed on glass slides, and dried at 50° C. for 1hour. The coated slides were then placed in baths containing a 0.5%solution of Palmolive Plus dishwashing fluid in water, and maintained at25° C. (i.e. below the T_(o) of the polymer), 53° C. (i.e. at about theT_(p) of the polymer) and 75° C. (i.e. well above the T_(p) of thepolymer). The baths were stirred gently and the slides were observed.

The Portion A film, at 25° C., separates from the slide after 30minutes, without swelling or blistering; when the film, after it hasseparated, is lifted out of the bath on the slide and dried, it remainsintact and transparent. The Portion A films, at 53° C. and 75° C., swelland blister, and separate from the slide after 25 minutes. When thefilms, after they have been separated, are lifted out of the baths onthe slides, and dried, they show some disintegration and are opaque.

The Portion B film, at 25° C., blisters and separates from the slideafter 30 minutes; after removal and drying, it remains intact andtransparent. The Portion B films, at 53° C. and 75° C., blister andbecome opaque and separate from the slides after 3 minutes; afterremoval and drying, they disintegrate completely.

Example 23

The procedure of Examples 18 and 19 were followed to generate a waterbased emulsion of SCC polymer. The milky white formulation was appliedto the hair of a doll through a pump spray bottle. The hair was thenheated with a hair dryer, evaporating the water and melting the SCCpolymer. While the polymer was in the molten state, the doll's hair wasshaped in a desired configuration.

When the doll's hair needed to be set in another configuration, the hairwas first reheated to melt the composition retained in the hair. Thehair was then reshaped in the new configuration. This process wasrepeated several times, and each time the doll's hair retained the newdesired configuration.

Example 24

Prospective Example

The procedure of Examples 18 or 19 is followed to generate a water basedemulsion of SCC polymer. Fabric is dip coated in the milky whiteformulation and allowed to dry. The dried fabric is placed in thedesired configuration and heated and pressed with an iron to melt theSCC polymer. The fabric is cooled in the desired configuration.

Examples 25-52

Examples 25-52 show the preparation and use of aqueous polymerdispersions for coating seeds.

The following additional abbreviations are used in these Examples TTT,1,3,5-triallyl triazine trione (crosslinker); BDE, 1,4-butanedioldivinyl ether (crosslinker); TETA, triethylene tetramine (externalcrosslinker); AH, 10% aqueous ammonium hydroxide available from Baxter;CC, calcium carbonate under the trade name Albaglos, 0.6 microns,available from Specialty Minerals; Zinplex 15 is available from Rohm andHaas (external crosslinker); DEAPA, N, N-Diethyl aminopropylamine isavailable from Aldrich (external crosslinker); Colloid 211 is a watersoluble polyacrylate polymer obtained from Rhone-Poulenc that acts as adispersant for the calcium carbonate; Defoamer 2010 is available fromDow Corning and is a low surface energy silicone polymer, and Seedmateseed colorant is a product of Loveland Industries Inc. NP, n-propanol(cosolvent).

The following is a surfactant: Lodyne S-106A, a fluorosurfactantavailable from Ciba-Geigy.

Examples 25-32 Preparation of Polymer Latex

A polymer latex for Example 25 was prepared by mixing together C16A (68g), C6A (27 g) , MA (5 g), C4DA (1 g), water (160 g), IPA (40 g), A-102(2 g), SLS-R (2 g), 15-S-7 (2 g) , 15-S-40 (0.5 g), and SBC (0.4 g) in abottle. The bottle was purged with N₂ for 30 min. The bottle was thencapped and heated to 70° C., and then PP (0.4 g) was added. The reactionwas carried out at 70° C. for 4 h. The reaction exothermed rapidly and ablue latex was formed. The latex was cooled and neutralized with aqueousammonia.

The latices of Examples 26, 27, and 28 were prepared in the same waydescribed for Example 1 with the same ingredients and amounts as in 25,except that TTT and BDE were substituted for C4DA in Examples 26 and 27,respectively. Example 28 was prepared in the absence of an internalcrosslinker. In Example 29 an internally crosslinked polymer wasprepared, where the crosslinking component was 1,4-butanedioldiacrylate. The monomers were mixed together: C16A (68 g), C6A (27 g),MA (5 g), 1,4-butanediol diacrylate (1 g). An aqueous phase was preparedwith water (160 g), isopropanol (40 g), Aerosol A-102 (4 g), CarsonolSLS-R (2 g), Tergitol 15-S-7 (2 g), Tergitol 15-S-40 (0.5 g), NaHCO₃(0.4 g), and potassium persulfate (0.4 g). The reagents were mixedtogether and purged with N₂ for 30 minutes in a bottle. The bottle wasthen capped and heated to 70° C., and 0.4 g of potassium persulfate wasadded. The reaction was carried out at 70° C. for 4 hours. The reactionexothermed rapidly and a blue latex was formed. The latex was cooled andneutralized with aqueous ammonia.

For Example 30 a polymer was prepared with 2-acrylamido-2-methylpropanesulfonic acid (AMPS). C16A (31.5 g), AMPS (6 g of a 50% aq. solution),water (80 g), isopropanol (20 g), Aerosol A-102 (2 g), Carsonol SLS-R (1g) were mixed together in a bottle and purged with N₂ for 20 min. Thebottle was then capped and heated to 80° C., and 0.4 g of potassiumpersulfate was added. The reaction was carried out at 80° C. for 3 h. Abluish tan emulsion was formed, cooled overnight and neutralized withammonium hydroxide.

For Example 31 a polymer was prepared in a glass lined Pflauder reactorby mixing C16A (6555 g), C6A (2470 g), MA (475 g), C6DA (66.5 g), SLS(190 g), A-102 (380 g), 15-S-7 (190 g), 15-S-40 (47.5 g), water (15,000g) and IPA (3800 g). The mixture was sparged with nitrogen for an hour.The contents of the reactor were raised to 65 C, and an initiatorsolution of 38 g potassium persulfate in 380 g water as added. Thereactor was maintained at 70 C for 2 hours. A chaser solution of 19 g ofpotassium persulfate in 380 g water was added and the reactor contentsmaintained at 70 C for an additional three hours, and cooled to roomtemperature. The latex was neutralized with AH and filtered through a 63micron wire mesh filter.

For Example 32, a polymer was prepared in a glass lined Pflauder reactorby mixing C14A (2158 g), C6A (312 g), AA (130 g), C6DA (18.2 g), SLS(52.2 g), A-102 (105.5 g), 15-S-7 (54.7 g), 15-S-40 (13 g), water (4,061g) and IPA (1045 g). The mixture was sparged with nitrogen for 30minutes. The contents of the reactor were raised to 65 C, and aninitiator solution of 10.4 g potassium persulfate in 104 g water asadded. The reactor was maintained at 70 C for 2 hours. A chaser solutionof 5.2 g of potassium persulfate in 104 g water was added and thereactor contents maintained at 70 C for an additional three hours, andcooled to room temperature. The latex was neutralized with AH andfiltered through a 63 micron wire mesh filter.

Example 33 Preparation of Seed Coating Formulations

Seed coating formulations were prepared that contained:

Type I. Polymer latex containing no internal or external crosslinker(using the latex of Example 28); Type II. Polymer latex with internalcrosslinks (using the latex of Example 25); Type III. Polymer latexprepared with an external crosslinker (using the latex of Example 28 inthe presence of Zn²⁺); and Type IV. Polymer latex with internal andexternal crosslinks (using the latex of Example 25 in the presence ofTETA).

The following procedure was followed to prepare formulations of Type Iand II:

A wet grind was prepared consisting of Colloid 211 (1 g), water (20 g),AH (10 g), polymer latex (100 g), and CC (120 g). The wet grind wasprepared in a Cowels mixer at 3000 rpm for 30 min (shear rate 126sec⁻¹). The let down was prepared by mixing (VIRTIS Shear mixing at 2000rpm for 10 min) and consisted of wet grind 125 g), polymer latex (550g), water (1200 g), and seed colorant (5 g). AH (10 g) was added to theformulation preparations. The let down was used directly to coat theseeds.

For Type III formulations, external crosslinker was added to the letdown prior to coating. For example, Zinplex 15 (2.3 g) was added to thetype I formulation during the let down (970 g) to form a coatingsolution. Type III formulations were prepared as follows:

CC (40 g) and water (100 g) were sheared in a VIRTIS at 2000 rpm, andColloid 211 (0.5 g) mixed with 3 ml water was slowly added and shearedfor 2 min. The latex (400 g equivalent to 120 g polymer) was made basicwith 10% AH, 4-5 ml and was slowly added followed by the Zinplex andDEAPA (both diluted with 2-3 ml of water) and sheared for about 5 min.Water (500 g) and red dye ( 3 ml) were added. The coating solution wasthen filtered through a 63 micron mesh filter. Towards the end of thefiltration 2 drops of defoamer were added.

For Type IV formulations, external crosslinker was added to the let-downduring its preparation. For example, TTM (2.4 g) was added to the typeII formulation let down (940 g) or Zinplex (8.6 g) was diluted with 20 gwater and added to the type II formulation let down (1895 g). Type IVformulations were prepared as follows:

A wet grind was prepared form Colloid 211 (2 g), water (20 g), aqueousAH (20 g), latex (250 g) and CC (360 g). The grind was mixed by blendingin a Cowels mixer at 3000 rpm for 30 min. A concentrate preparation wasmade from wet grind (650 g), latex (2150 g), Zinplex 15 (18. 4 g), andSeedmate Colorant (25 g). The coating solution was prepared by dilutingthe concentrate (540 g) with water (880 g).

All of these formulations have a T_(m) of about 19-21° C.

Examples 34-46 Seed Testing

Seed Coating Procedure

Seeds were coated with the formulations of Example 33 using seed coatingequipment for water based coatings manufactured by Diamond CoatingEquipment (Tucson, Ariz.). The seed coating equipment consisted of aperforated pan fitted with baffles, and capable of handling about 20 lbsof seed/batch. The seeds were coated with a fine spray of theformulation from a spray nozzle located in the coating pan. To assist indrying of the seeds the coater was equipped with a hot air inlet and anair exhaust.

An exemplary coating procedure involving soybeans utilized Soybeans (6kg), which were loaded into the seed coating equipment. The coatingformulation was pumped to the spray nozzle using a peristaltic pump. Thepan was rotated at a rate of 12-13 rpm to keep the seeds thoroughlymixed. The coating was started by turning the spray nozzle onpneumatically, and pumping at a rate of 30 ml/min. The pan temperaturewas maintained at 30° C. and the coating was carried out for 17 min. Thespray nozzle was shut off, the pan rotation stopped, and the coatedseeds were removed.

Seed Testing

Seeds were tested for water uptake and germination/plant emergence as afunction of temperature under controlled conditions. The testing methodsused are similar to those prescribed by the Association of Seed Analysts(AOSA) testing methods, and Rules of Testing Seeds (Association ofOfficial Seed Analysts. Journal of Seed Technology, Vol 12, No: 3,1988). The performance of the coated soybean seeds were measured by thewater uptake of the seeds at two temperatures at 10 and 25° C. at 48 h,and the germination of the seeds at 25° C. for 7 days, and at 10° C. for7 days followed by 7 days at 25° C. Table 2 gives the water uptake ofrepresentative coatings along with the water uptake of the uncoated seed(Example 34) used as a control.

Paper Towel Germination Test

Germination paper sheets [Anchor #38 and #76 seed germination paper(254×381 mm)] were allowed to equilibrate for about 30 min withapproximately two times their dry weight of water.

Two moistened sheets were placed on the benchtop, and 10 g of seeds wereplaced along the length of the paper, about a third of the length fromthe top. Another wet sheet of paper was placed on top. A hem about 25 mmwide at the bottom was folded and the sheets rolled, and set vertically.Four to five such paper dolls were secured loosely with a pair of rubberbands and were placed vertically in a plastic bag and placed inincubators maintained at 10° C. and 25° C., respectively. After thespecified amount of time (48 hours), the seeds were removed and weighed.

TABLE 2 % Water % Water Coating Uptake Uptake Example Type Polymer LatexType at 10° C. at 25° C. 34 Control No coating No 102  120  coating 35II C16A/C6A/ Internal 11 80 AA/C14DA X-linker (68/27/5/1) 36 IVC16A/C6A/ Int, and 13 92 AA/C14DA 0.5% Zn (68/27/5/1) External 37 IVC16A/C6A/ Int. and 20 99 AA/C14DA 2% TETA (68/27/5/1) 38 IV C16A/C6A/Int. 1% 18 82 AA/C14DA Zn Ext (68/27/5/1.5) 39 IV C16A/C6A/ Int. 1.5% 3092 AA/C14DA Zn Ext (68/27/5/1.5) 40 IV C16A/C6A/ Int. 0.5% 25 84MA/C14DA Zn Ext (68/27/5/1) 41 II C16A/C6A/ Int. 15 68 MA/C14DA no Ext(68/27/5/1) 42 IV C16A/C6A/ Int. 0.5% 27 93 AA/C14DA Zn Ext (68/27/3/1)43 III C16A/C6A/ No Int. 36 97 AA 0.5% (68/27/7.5) Zn Ext 44 IIC16A/C6A/ Int. 20 96 AA/C4DA no Ext (68/27/5/1) 45 I C16A/C6A/ No Int.36 48 MA/ No Ext 68/27/7.5 46 III C16A/C6A/ No Int. 36 40 MA/ 0.5%68/27/7.5 Zn Ext

As illustrated in the Table 2 the presence of an internal crosslinker(types II and IV) decreased the amount of water uptake at lowtemperatures (10° C.) and increased the water uptake at highertemperatures (25° C.) because the seed coating fell apart more easilyonce the seeds started expanding. The presence of an externalcrosslinker improved the mechanical stability of the seed coating. Thusa combination of external and internal crosslinkers can be employed toselect the water permeabilities of water coatings at varioustemperatures.

Example 47

A wet grind consisting of Colloid 211 (0.4 g), ammonia (0.2 g, 50/50v/v), water (190 g) and CaCO₃ (330 g) was blended in a Cowels mixer at3000 rpm for 30 min. The wet grind (172 g) was mixed with the polymerlatex of Example 7(C16A/C6A/MA/C6DA, 70/25/5/0.5) (705 g) (T_(m) of 20to 21° C.) in a VIRTIS mixer. Zinplex 15 (5.4 g diluted with 20 g water)was added slowly into the formulation followed by Lodyne S-106A (2.5 gdiluted with 20 g water). Seed colorant (8 g), and water (540 g) wereadded to complete the formulation. The coating solution was filteredthrough a 60 micron wire mesh filter. Hybrid Corn (4 kg) was loaded intothe seed coater, and the coating was carried out at a flow rate of 60mL/min for a period of 11 min. The internal temperature of the pan waskept at ° 40° C.

Example 48

A wet grind was prepared by mixing in a Cowels mixer Colloid 211 (2 g),ammonium hydroxide (40 g of 10% aq. solution), the polymer latexC16A/C6A/MA/C6DA (70/25/5/0.5)) (250 g) (T_(m) of 20 to 21° C.), andCaCO₃ (360 g) for 30 min at 3000 rpm. The concentrate was prepared fromthe wet grind by mixing the wet grind with the polymer latex (2150 g),and 20 g of 10% aq. ammonia. The coating solution was prepared bycombining under light shear the concentrate (550 g), water (850 g),Zinplex 15 (3.6 g with 20 g water), and the seed colorant (10 g). Threekg of seeds were coated at a flow rate of 40 mL/min for 30 min. The pantemperature was maintained at 30° C.

Example 49

The formulation of Example 48 was used for coating wheat. The coatingwas carried out at 40 mL/min for a period of 20 min, with a pantemperature of 35° C.

Example 50

The polymer latex of Example 15(C14A/C6A/MA/C6DA (80/15/5/0.7)) with alower T_(m) (12° C.) was used in the coating of sugarbeets. All othercomponents of the formulation were identical to those described forExample 46. Sugarbeets (4 kg) were coated at a spray rate of 30 mL/min,and a pan temperature of 30° C. were coated for 40 min.

Example 51

A wet grind was prepared by blending Colloid 211 (2 g), ammonia (40 g,10% aq. solution), latex (250 g) (C16A/C6A/AA/C14DA (70/25/8/1)), andCaCO₃ (360 g). A concentrate was prepared by mixing the wet grind withthe polymer latex (2150 g) in a VIRTIS mixer, followed by 18.4 g. Thecottonseeds (4 kg) were coated at a flow rate of 30 mL/min for 45 minwith the pan temperature not exceeding 30° C.

Coatings on other seed varieties, including lentils, chickpeas and sweetcorn, were prepared using similar formulations as described above.

Example 52

Two hybrid corn varieties from Sucrosco Seeds (Manilla, Iowa) were fieldtested. They were planted in Casey, Iowa. Prior to planting some of theseeds were left uncoated, other were coated with (C16A/C6A/MA/C6DA(70/25/5/0.5), 1% Zinplex) (Example 52A) or (C16A/C6A/MA/C6DA(70/25/5/0.5), 0.5% Zinplex) (Example 52B). Seed were planted atdifferent times (Mar. 23, Apr. 3, and Apr. 17, 1996) and stand countswere performed 3 weeks after planting. The results are shown in Table 3and are the average of four different experiments.

TABLE 3 Hybrid Uncoated Example 52A Example 52B Planting Corn (standCoating (stand Coating (stand Date Variety count) count) count) 23 MarchA 1.8  19  51 23 March B 23  44  69 3 April A 74  91 102 3 April B 110111 114 17 April A 106 115 104 17 April B 110 119 121

As can be seen from Table 3, coating the seeds with the polymer latexcoatings protect the seeds when the seeds are planted early in theplanting season when there is a possibility for the seeds to sufferchilling injury. When seeds are planted later in the planting season,i.e., when it is unlikely for the soil temperature to go below 0° C.,the seed coating does not have an adverse effect on corn germinationbecause the seed coating is readily released if the temperature remainsabove the T_(m) of the seed coating polymer and the seed startsexpanding.

What is claimed is:
 1. A fibrous substrate having a solid polymericcoating thereon, the coating having been obtained by (1) applying to thefibrous substrate a composition which comprises water and, suspended inthe water, 2-50% by weight, based on the weight of the composition, ofsolid particles consisting essentially of a crosslinked side chaincrystalline (SCC) polymer, the polymer (a) having a melting point T_(m)of at least 20° C., and an onset-of-melting temperature T_(o) such that(T_(m)−T_(o)) is less than 20° C., (b) having a gel content of at least50%, and (c) being derived from a monomer component consisting of: (i)90 to 98% by weight of a hydrophobic monomer component which consists ofone or more hydrophobic monomers each having a solubility in water at25° C. of less than 2% by weight and which comprise at least onehydrophobic monomer such that a homopolymer thereof is an SCC polymer;and (ii) 10 to 2% by weight of a hydrophilic monomer component whichconsists of one or more hydrophilic monomers each having a solubility inwater at 25° C. of at least 2% by weight; at least one of thehydrophobic monomer component and the hydrophilic monomer componentcomprising a crosslinking monomer having at least two polymerizablegroups; and (2) evaporating water from the dispersion to form the solidpolymeric coating.
 2. A substrate according to claim 1 wherein(T_(m)−T_(o)) is less than 10° C.
 3. A composition which comprises: (1)water, (2) suspended in the water, 2-50% by weight, based on the weightof the composition, of solid particles consisting essentially of acrosslinked side chain crystalline (SCC) polymer which (a) has a meltingpoint T_(m) of at least 20° C. and an onset-of-melting temperature T_(o)such that (T_(m)−T_(o)) is less than 20° C., (b) has a gel content of atleast 50%, (c) is derived from a monomer component consisting of: (i) 90to 98% by weight of a hydrophobic monomer component which consists ofone or more hydrophobic monomers each having a solubility in water at25° C. of less than 2% by weight and which comprises at least onehydrophobic monomer such that a homopolyer thereof is an SCC polymer;and (ii) 10 to 2% by weight of a hydrophilic monomer component whichconsists of one or more hydrophilic monomers each having a solubility inwater at 25° C. of at least 2% by weight; at least one of thehydrophobic monomer component and the hydrophilic monomer componentcomprising a crosslinking monomer having at least two polymerizablegroups; and (d) contains less than 1% by weight of unreacted monomer;and (3) a surfactant.
 4. A composition according to claim 3 wherein thehydrophobic monomer component comprises, in addition to said firsthydrophobic monomer such that homopolymer thereof is an SCC polymer, asecond hydrophobic monomer which (a) is such that a homopolymer thereofis amorphous and has a glass transition point T_(g) which is less thanT_(c), where T_(c) is the melting point of the homopolyer of the firsthydrophobic monomer, and (b) is present in amount such that T_(m) is(T_(c)−5)° C. or less.
 5. A composition according to claim 3 wherein thehydrophobic monomer component comprises, in addition to the firsthydrophobic monomer such that homopolymer thereof is an SCC polymer, asecond hydrophobic monomer which (a) is such that a homopolymer thereofis amorphous and has a glass transition point T_(g) which is more thanT_(c), where T_(c) is the melting point of the homopolyer of the firsthydrophobic monomer, and (b) is present in amount such that a coatingformed from the composition has a tack at (T_(c)+10)° C. which is lessthan the tack at (T_(c)+10)° C. of a coating formed under the sameconditions from a composition which is identical except that thecrystalline polymer does not contain units derived from the secondhydrophobic monomer.
 6. A composition according to claim 3 wherein thesolid particles have an average particle size of less than 0.5 micron.7. A composition according to claim 3 which is suitable for use insetting a flexible fabric and which also contains at least 0.1% byweight of a fabric-treating additive.
 8. A composition according toclaim 3 which is suitable for setting human hair, wherein thecrystalline polymer has a T_(m) of 40 to 60° C., and the additive is ahair care additive.
 9. A composition according to claim 3 wherein theSCC polymer has a gel content of 60 to 100%.
 10. A composition accordingto claim 3, which contains less than 1% of unreacted monomer, based onthe weight of the polymer.
 11. A composition according to claim 3,wherein at least some of the polymer particles comprise a corecomprising said crystalline polymer and a coating around the corecomprising a substantially amorphous polymer.
 12. A method of providinga solid polymeric coating on a flexible fibrous material, the methodcomprising: (A) applying to the fibrous material a composition whichcomprises: (1) water, (2) suspended in the water, 2-50% by weight, basedon the weight of the composition, of solid particles consistingessentially of a crosslinked side chain crystalline (SCC) polymer which(a) has a melting point T_(m) of at least 20° C., and anonset-of-melting temperature T_(o) such that (T_(m)−T_(o)) is less than20° C., (b) has a gel content of at least 50%, (c) is derived from amonomer component consisting of: (i) 90 to 98% by weight of ahydrophobic monomer to component which consists of one or morehydrophobic monomers each having a solubility in water at 25° C. of lessthan 2% by weight and which comprises at least one hydrophobic monomersuch that a homopolymer thereof is an SCC polymer; and (ii) 10 to 2% byweight of a hydrophilic monomer component which consists of one or morehydrophilic monomers each having a solubility in water at 25° C. of atleast 2% by weight; at least one of the hydrophobic monomer componentand the hydrophilic monomer component comprising a crosslinking monomerhaving at least two polymerizable groups; and (d) contains less than 1%by weight of unreacted monomer; and (3) a surfactant; and (B)evaporating the water from the composition while the composition is incontact with the fibrous material, thereby forming a coating on thefibrous material.
 13. A method according to claim 12, wherein step (B)is carried out under conditions such that the particles coalesce to forma continuous coating which retains a particulate character and whosepermeability to water above T_(m) is at least three times itspermeability to water below T_(m).
 14. A method according to claim 12,which further comprises the steps of (C) while the coating is at atemperature above T_(m), setting the fibrous material into a firstdesired configuration; (D) cooling the coating below T_(m) whilemaintaining the fibrous material in the first desired configuration; (E)re-heating the coating to a temperature greater than T_(m); (F) afterre-heating the coating, and while the coating is at a temperature aboveT_(m), setting the fibrous material into a second desired configurationwhich is the same as or different from the first desired configuration;and (G) cooling the coating while maintaining the fibrous material inthe second desired configuration.
 15. A method of providing a solidpolymeric coating on a flexible fibrous material, the method comprising:(A) applying to the fibrous material a composition which comprises: (1)water, (2) suspended in the water, 2-50% by weight, based on the weightof the composition, of solid particles consisting essentially of a sidechain crystalline (SCC) polymer which (a) has a melting point T_(m) ofat least 20° C., and an onset-of-melting temperature T_(o) such that(T_(m)−T_(o)) is less than 20° C., (b) is derived from a monomercomponent consisting of: (i) 90 to 98% by weight of a hydrophobicmonomer component which consists of one or more hydrophobic monomerseach having a solubility in water at 25° C. of less than 2% by weightand which comprises at least one hydrophobic monomer such that ahomopolymer thereof is an SCC polymer; and (ii) 10 to 2% by weight of ahydrophilic monomer component which consists of one or more hydrophilicmonomers each having a solubility in water at 25° C. of at least 2% byweight; (3) 0.1 to 10% by weight, based on the weight of the monomercomponent, of an external crosslinking agent; and (4) a surfactant, and(B) evaporating the water from the composition while the composition isin contact with the fibrous material, thereby forming a coating on thefibrous material; the external crosslinking agent, the polymer formed instep (A), and the conditions in step (A) and step (B) being such thatduring one or both of step (A) and step (B), interaction between groupson the polymer and groups on the external crosslinking agent or on aproduct formed from the crosslinking agent hardens the polymer particlesso that, in step (B), the particles coalesce to form a continuouscoating but retain a particulate character.
 16. A method according toclaim 15 wherein (T_(m)−T_(o)) is less than 10° C.
 17. A methodaccording to claim 15 wherein the hydrophobic monomer componentcomprises, in addition to said first hydrophobic monomer such thathomopolymer thereof is an SCC polymer, a second hydrophobic monomerwhich (a) is such that a homopolymer thereof is amorphous and has aglass transition point T_(g) which is less than T_(c), where T_(c) isthe melting point of the homopolymer of the first hydrophobic monomer,and (b) is present in amount such that T_(m) is (T_(c)−5)° C. or less.18. A composition according to claim 15 wherein the hydrophobic monomercomponent comprises, in addition to the first hydrophobic monomer suchthat homopolymer thereof is an SCC polymer, a second hydrophobic monomerwhich (a) is such that a homopolymer thereof is amorphous and has aglass transition point T_(g) which is more than T_(c), where T_(c) isthe melting point of the homopolymer of the first hydrophobic monomer,and (b) is present in amount such that a coating formed from thecomposition has a tack at (T_(c)+10)° C. which is less than the tack at(T_(c)+10)° C. of a coating formed under the same conditions from acomposition which is identical except that the crystalline polymer doesnot contain units derived from the second hydrophobic monomer.
 19. Amethod according to claim 15, wherein the solid particles have anaverage particle size of less than 0.5 micron.
 20. A method according toclaim 15 wherein the flexible fibrous material is a flexible fabric andthe composition also contains at least 0.1% by weight of a fabrictreating additive.
 21. A method according to claim 15 wherein theflexible fibrous material is human hair, the crystalline polymer has aT_(m) of 40 to 60° C., and the composition also contains a hair careadditive.